Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02377782 2007-10-05
LOW-CARBON STEELS OF SUPERIOR
MECHANICAL AND CORROSION PROPERTIES
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention resides in the field of steel alloys, particularly those of
high strength,
toughness, corrosion resistance, and cold formability, and also in the
technology of the
processing of steel alloys to form microstructures that provide the steel with
particular
physical and chemical properties.
2. Description of the Prior Art
Steel alloys of high strength and toughness and cold formability whose
microstructures
are composites of martensite and austenite phases are disclosed in the
following United States
patents (all assigned to The Regents of the University of California):
4,170,497 (Gareth Thomas and Bangaru V. N. Rao),
issued October 9, 1979 on an application filed August 24, 1977
4,170,499 (Gareth Thomas and Bangaru V. N. Rao),
issued October 9, 1979 on an application filed September 14, 1978 as a
continuation- in-part of the above application filed on August 24, 1977
4,619,714 (Gareth Thomas, Jae-Hwan Ahn, and Nack-Joon Kim), issued October 28,
1986 on an application filed November 29, 1984, as a continuation-in-part of
an application filed on August 6, 1984
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4,671,827 (Gareth Thomas, Nack J. Kim, and Ramamoorthy Ramesh),
issued June 9, 1987 on an application filed on October 11, 1985
The microstructure plays a key role in establishing the properties of a
particular steel alloy, and thus strength and toughness of the alloy depend
not only on the
selection and amounts of the alloying elements, but also on the crystalline
phases present
and their arrangement. Alloys intended for use in certain environments require
higher
strength and toughness, and in general a combination of properties that are
often in
conflict, since certain alloying elements that contribute to one property may
detract from
another.
The alloys disclosed in the patents listed above are carbon steel alloys that
have microstructures consisting of laths of martensite alternating with thin
films of
austenite and dispersed with fine grains of carbides produced by
autotempering. The
arrangement in which laths of one phase are separated by thin films of the
other is
referred to as a "dislocated lath" structure, and is formed by first heating
the alloy into the
austenite range, then cooling the alloy below a phase transition temperature
into a range
in which austenite transforms to martensite, accompanied by rolling to achieve
the
desired shape of the product and to refine the alternating lath and thin film
arrangement.
This microstructure is preferable to the alternative of a twinned martensite
structure, since
the lath structure has a greater toughness. The patents also disclose that
excess carbon in
the lath regions precipitates during the cooling process to form cementite
(iron carbide,
Fe3C) by a phenomenon known as "autotempering." These autotempered carbides
are
believed to contribute to the toughness of the steel.
The dislocated lath structure produces a high-strength steel that is both
tough and ductile, qualities that are needed for resistance to crack
propagation and for
sufficient formability to permit the successful fabrication of engineering
components
from the steel. Controlling the martensite phase to achieve a dislocated lath
structure
rather than a twinned structure is one of the most effective means of
achieving the
necessary levels of strength and toughness, while the thin films of retained
austenite
contribute the qualities of ductility and formability. Achieving this
dislocated lath
microstructure rather than the less desirable twinned structure requires a
careful selection
of the alloy composition, since the alloy composition affects the martensite
start
temperature, commonly referred to as MS, which is the temperature at which the
martensite phase first begins to form. The martensite transition temperature
is one of the
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factors that determine whether a twinned structure or a dislocated lath
structure will be formed
during the phase transition.
In many applications, the ability to resist corrosion is highly important to
the success
of the steel component. This is particularly true in steel-reinforced concrete
in view of the
porosity of concrete, and in steel that is used in moist environments in
general. In view of the
ever-present concerns about corrosion, there is a continuing effort to develop
steel alloys with
improved corrosion resistance. These and other matters in regard to the
production of steel of
high strength and toughness that is also resistant to corrosion are addressed
by the present
invention.
SUMMARY OF THE INVENTION
It has now been discovered that corrosion in a dislocated lath structure can
be reduced
by eliminating the presence of precipitates such as carbides, nitrides, and
carbonitrides from
the structure, including those that are produced by autotempering and also
including
transformation products such as bainite and pearlite containing carbides,
nitrides or
carbonitrides of different morphologies depending on composition, cooling
rate, and other
parameters of the alloying process. It has been discovered that the interfaces
between the
small crystals of these precipitates and the martensite phase through which
the precipitates are
dispersed promote corrosion by acting as galvanic cells, and that pitting of
the steel begins at
these interfaces. Accordingly, there is disclosed an alloy steel with a
dislocated lath
microstructure that does not contain carbides, nitrides or carbonitrides, as
well as a method for
forming an alloy steel of this microstructure. It has been discovered that
this type of
microstructure can be achieved by limiting the choice and the amounts of the
alloying
elements such that the martensite start temperature MS is 350 C or greater. It
has also been
discovered that while autotempering and other means of carbide, nitride or
carbonitride
precipitation in a dislocated lath structure can be avoided by a rapid cooling
rate, certain alloy
compositions will produce a dislocated lath structure free of autotempered
products and
precipitates in general simply by air cooling.
In accordance with one aspect of the invention, there is provided a process
for
manufacturing a high-strength, corrosion-resistant, tough alloy carbon steel.
The process
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involves heating an alloy composition, the alloy composition consisting of
iron and at least
one alloying element comprising carbon in proportions such that the alloy
composition has a
martensite transition range having a martensite start temperature MS of at
least about 350 C,
and such that air-cooling of the alloy composition through the martensite
transition range
without forming carbides is permitted, to a temperature sufficiently high to
cause
austenitization of the alloy composition, under conditions causing the alloy
composition to
assume a homogeneous austenite phase with all alloying elements in solution.
The process
also involves cooling the homogeneous austenite phase through the martensite
transition range
at a cooling rate sufficiently fast to avoid the occurrence of autotempering,
to achieve a
microstructure containing laths of martensite alternating with films of
retained austenite, and
containing substantially no carbides.
The carbon may constitute from about 0.01% to about 0.35% by weight of the
alloy
composition.
The carbon may constitute from about 0.05% to about 0.20% by weight of the
alloy
composition.
The carbon may constitute from about 0.02% to about 0.15% by weight of the
alloy
composition.
The at least one alloying element may further include chromium in an amount
from
about 1% to about 13% by weight of the alloy composition.
The chromium may constitute from about 6% to about 12% by weight of the alloy
composition.
The chromium may constitute from about 8% to about 10% of the alloy
composition.
The at least one alloying element may further include silicon to a maximum of
about
2.0% by weight of the alloy composition.
The silicon may constitute from about 0.5% to about 2.0% by weight of the
alloy
composition.
The at least one alloying element may further include nitrogen, and the
cooling rate
may be sufficiently fast to achieve a microstructure containing laths of
martensite alternating
with films of retained austenite and may contain substantially no carbides,
nitrides, or
carbonitrides.
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The heating may be performed at a temperature within the range of from about
900 C
to about 1150 C.
The heating may be performed at a temperature of a maximum of about 1150 C.
The films of retained austenite may constitute from about 0.5% to about 15% of
the
microstructure.
The films of retained austenite may constitute from about 3% to about 10% of
the
microstructure.
The films of retained austenite may constitute a maximum of about 5% of the
microstructure.
The carbon may constitute from about 0.05% to about 0.1% by weight of the
alloy
composition and the at least one alloying element may further include (i) a
member selected
from the group consisting of silicon and chromium at a concentration of at
least about 2% by
weight and (ii) manganese at a concentration of at least about 0.5% by weight,
and the cooling
is performed by quenching in water.
The carbon may constitute from about 0.05% to about 0.1% by weight of the
alloy
composition and the at least one alloying element may further include (i) a
member selected
from the group consisting of silicon and chromium at a concentration of about
2% by weight
and (ii) manganese at a concentration of about 0.5% by weight, and the cooling
is performed
by quenching in water.
The carbon may constitute from about 0.03% to about 0.05% by weight of the
alloy
composition and the at least one alloying element may further include (i)
chromium at a
concentration of from about 8% to about 12% by weight and (ii) manganese at a
concentration
of from about 0.2% to about 0.5% by weight, and the cooling is performed by
air cooling.
In accordance with another aspect of the invention, there is provided a
product
manufactured by the process.
In accordance with another aspect of the invention, there is provided a
product
manufactured by the process and including from about 0.05% to about 0.2% by
weight carbon
and from about 6% to about 12% by weight chromium.
In accordance with another aspect of the invention, there is provided a
product
manufactured by the process and including from about 0.05% to about 0.2% by
weight carbon
and up to about 2% by weight silicon.
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In accordance with another aspect of the invention, there is provided a
product
manufactured by the process wherein heating is performed at a maximum
temperature of
about 1150 C and the films of retained austenite constitute a maximum of about
5% of the
microstructure.
These and other objects, features, and advantages of the invention will be
better
understood by the description that follows.
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BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a phase transformation kinetic diagram demonstrating the alloy
processing procedures and conditions of this invention.
FIG. 2 is a sketch representing the microstructure of the alloy composition
of this invention.
FIG. 3 is a plot of stress vs. strain for four alloys in accordance with this
invention.
DESCRIPTION OF THE SPECIFIC EMBODIMENTS
Autotempering of an alloy composition occurs when a phase that is under
stress due to supersaturation with an alloying element is relieved of its
stress by
precipitating the excess amount of the alloying element as a compound with
another
element of the alloy composition in such a manner that the resulting compound
resides in
isolated regions dispersed throughout the phase while the remainder of the
phase reverts
to a saturated condition. Autotempering will thus cause excess carbon to
precipitate as
iron carbide (Fe3C). If chromium is present as an additional alloying element,
some of
the excess carbon may also precipitate as trichromium dicarbide (Cr3C2), and
similar
carbides may precipitate with other alloying elements. Autotempering will also
cause
excess nitrogen to precipitate as either nitrides or carbonitrides. All of
these precipitates
are collectively referred to herein as "autotempering (or autotempered)
products" and it is
the avoidance of these products and other transformation products that include
precipitates that is achieved by the present invention as a means of
accomplishing its goal
of lessening the susceptibility of the alloy to corrosion.
The avoidance of the formation of autotempered products and carbides,
nitrides and carbonitrides in general is achieved in accordance with this
invention by
appropriate selection of an alloy composition and a cooling rate through the
martensite
transition range. The phase transitions that occur upon cooling an alloy from
the
austenite phase are governed by the cooling rate at any particular stage of
the cooling, and
the transitions are commonly represented by phase transformation kinetic
diagrams with
temperature as the vertical axis and time as the horizontal axis, showing the
different
phases in different regions of the diagram, the lines between the regions
representing the
conditions at which transitions from one phase to another occur. The locations
of the
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boundary lines in the phase diagram and thus the regions that are defined by
the boundary
lines vary with the alloy composition.
An example of such a phase diagram is shown in FIG. 1. The martensite
transition range is represented by the area below a horizontal line 11 which
represents the
martensite start temperature M, and the region 12 above this line is the
region in which
the austenite phase prevails. A C-shaped curve 13 within the region 12 above
the MS line
divides the austenite region into two subregions. The subregion 14 to the left
of the "C"
is that in which the alloy remains entirely in the austenite phase, while the
subregion 15 to
the right of the "C" is that in which autotempered products and other
transformation
products that contain carbides, nitrides or carbonitrides of various
morphologies, such as
bainite and pearlite, form within the austenite phase. The position of the MS
line and the
position and curvature of the "C" curve will vary with the choice of alloying
elements and
the amounts of each.
The avoidance of the formation of autotempering products is thus achieved
by selecting a cooling regime which avoids intersection with or passage
through the
autotempered products subregion 15 (inside the curve of the "C"). If for
example a
constant cooling rate is used, the cooling regime will be represented by a
straight line that
is well into the austenite regime 14 at time zero and has a constant
(negative) slope. The
upper limit of cooling rates that will avoid the autotempered products
subregion 15 is
represented by the line 16 in the Figure which is tangential to the "C" curve.
To avoid the
formation of autotempered products or carbides in general, a cooling rate must
be used
that is represented by a line to the left of the limit line 16 (i.e., one
starting at the same
time-zero point but having a steeper slope).
Depending on the alloy composition, therefore, a cooling rate that is
sufficiently great to meet this requirement may be one that requires water
cooling or one
that can be achieved with air cooling. In general, if the levels of certain
alloying elements
in an alloy composition that is air-coolable and still has a sufficiently high
cooling rate
are lowered, it will be necessary to raise the levels of other alloying
elements to retain the
ability to use air cooling. For example, the lowering of one or more of such
alloying
elements as carbon, chromium, or silicon may be compensated for by raising the
level of
an element such as manganese.
Alloy compositions for example that contain (i) from about 0.05% to about
0.1 % carbon, (ii) either silicon or chomium at a concentration of at least
about 2%, and
(iii) manganese at a concentration of at least about 0.5%, all by weight (the
remainder
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being iron), are preferably cooled by a water quench. Specific examples of
these alloy
compositions are (A) an alloy in which the alloying elements are 2% silicon,
0.5%
manganese, and 0.1 % carbon, and (B) an alloy in which the alloying elements
are 2%
chromium, 0.5% manganese, and 0.05% carbon (all by weight with iron as the
remainder). Examples of alloy compositions that can be cooled by air cooling
while still
avoiding the formation of autotempered products are those that contain as
alloying
elements about 0.03% to about 0.05% carbon, about 8% to about 12% chromium,
and
about 0.2% to about 0.5% manganese, all by weight (the remainder being iron).
Specific
examples of these alloy compositions are (A) those containing 0.05% carbon, 8%
chromium, and 0.5% manganese, and (B) those containing 0.03% carbon, 12%
chromium, and 0.2% manganese. It is emphasized that these are only examples.
Other
alloying compositions will be apparent to those skilled in the art of steel
alloys and those
familiar with steel phase transformation kinetic diagrams.
As stated above, the avoidance of twinning during the phase transition is
achieved by using an alloy composition that has a martensite start temperature
MS of
about 350 C or greater. A preferred means of achieving this result is by use
of an alloy
composition that contains carbon as an alloying element at a concentration of
from about
0.01% to about 0.35%, more preferably from about 0.05% to about 0.20%, or from
about
0.02% to about 0.15%, all by weight. Examples of other alloying elements that
may also
be included are chromium, silicon, manganese, nickel, molybdenum, cobalt,
aluminum,
and nitrogen, either singly or in combinations. Chromium is particularly
preferred for its
passivating capability as a further means of imparting corrosion resistance to
the steel.
When chromium is included, its content may vary, but in most cases chromium
will
constitute an amount within the range of about 1% to about 13% by weight. A
preferred
range for the chromium content is about 6% to about 12% by weight, and a more
preferred range is about 8% to about 10% by weight. When silicon is present,
its
concentration may vary as well. Silicon is preferably present at a maximum of
about 2%
by weight, and most preferably from about 0.5% to about 2.0% by weight.
The processing procedures and conditions set forth in the four Thomas et
al. U.S. patents referenced above including existing bar and rod mill practice
may be used
in the practice of the present invention for the heating of the alloy
composition to the
austenite phase, the cooling of the alloy from the austenite phase through the
martensite
transition region, and the rolling of the alloy at one or more stages of the
process. In
accordance with these procedures, the heating of the alloy composition to the
austenite
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phase is preferably performed at a temperature up to about 1150 C, or more
preferably
within the range of from about 900 C to about 1150 C. The alloy is then held
at this
austenitization temperature for a sufficient period of time to achieve
substantially full
orientation of the elements according to the crystal structure of the
austenite phase.
Rolling is performed in a controlled manner at one or more stages during the
austenitization and cooling procedures to deform the crystal grains and store
strain energy
into the grains, and to guide the newly forming martensite phase into a
dislocated lath
arrangement of martensite laths separated by thin films of retained austenite.
Rolling at
the austenitization temperature aids in the diffusion of the alloying elements
to form a
homogeneous austenite crystalline phase. This is generally achieved by rolling
to
reductions of 10% or greater, and preferably to reductions ranging from about
30% to
about 60%.
Partial cooling followed by further rolling may then take place, guiding the
grains and crystal structure toward the dislocated lath arrangement, followed
by final
cooling in a manner that will achieve a cooling rate that avoids regions in
which
autotempered or transformation products will be formed, as described above.
The
thicknesses of the dislocated laths of martensite and the austenite films will
vary with the
alloy composition and the processing conditions and are not critical to this
invention. In
most cases, however, the retained austenite films will constitute from about
0.5% to about
15% by volume of the microstructure, preferably from about 3% to about 10%,
and most
preferably a maximum of about 5%. FIG. 2 is a sketch of the dislocated lath
structure of
the alloy, with substantially parallel laths 21 consisting of grains of
martensite-phase
crystals, the laths separated by thin films 22 of retained austenite phase.
Notable in this
structure is the absence of carbides and of precipitates in general (including
nitrides and
carbonitrides), which appear in the prior art structures as additional needle-
like structures
of a considerably smaller size scale than the two phases shown and dispersed
throughout
the dislocated martensite laths. The absence of these precipitates contributes
significantly
to the corrosion resistance of the alloy. The desired microstructure is also
obtained by
casting such steels, and by cooling at rates fast enough to achieve the
microstructure
depicted in FIG. 2, as stated above.
FIG. 3 is a plot of stress vs. strain for the microstructures of four alloys
within the scope of the present invention, all four of which are of the
dislocated lath
arrangement and free of autotempered products. Each alloy has 0.05% carbon,
with
varying amounts of chromium, the squares representing 2% chromium, the
triangles 4%,
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the circles 6% and the smooth line 8%. The area under each stress-strain curve
is a
measure of the toughness of the steel, and it will be noted that each increase
in the
chromium content produces an increase in the area and hence the toughness, and
yet all
four chromium levels exhibit a curve with substantial area underneath and
hence high
toughness.
The steel alloys of this invention are particularly useful in products that
require high tensile strengths and are manufactured by processes involving
cold forming
operations, since the microstructure of the alloys lends itself particularly
well to cold
forming. Examples of such products are sheet metal for automobiles and wire or
rods
such as for radially reinforced automobile tires.
The foregoing is offered primarily for purposes of illustration. Further
modifications and variations of the various parameters of the alloy
composition and the
processing procedures and conditions may be made that still embody the basic
and novel
concepts of this invention. These will readily occur to those skilled in the
art and are
included within the scope of this invention.
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